KR20070009559A - Impact-modified compositions and method - Google Patents

Abstract

The present invention relates to a composition comprising (i) at least one polycarbonate; (ii) optionally, at least one additional thermoplastic resin different from polycarbonate; and (iii) at least one rubber modified thermoplastic resin comprising a discontinuous elastomeric phase dispersed in a rigid thermoplastic phase, wherein at least a portion of the rigid thermoplastic phase is grafted to the elastomeric phase, and wherein the rigid thermoplastic phase comprises structural units derived from at least one vinyl aromatic monomer, at least one monoethylenically unsaturated nitrile monomer, and at least one monomer selected from the group consisting of (C1-C12)alkyl- and aryl-(meth) acrylate monomers. Articles made from the composition and a method for preparing the composition are also provided. ® KIPO & WIPO 2007

Description

IMPACT-MODIFIED COMPOSITIONS AND METHOD

The present invention relates to a composition comprising a polycarbonate and a rubber-modified thermoplastic resin.

Compositions comprising polycarbonates and rubber-modified thermoplastics are known in the art. These compositions often have the problem of collar formation during processing or use at high temperatures. A problem to be solved is to design compositions comprising polycarbonates and rubber-modified thermoplastics to have color stability under high temperature conditions.

Summary of the Invention

The present invention has found a composition comprising a polycarbonate and a rubber-modified thermoplastic resin that exhibits a surprising reduction in collar formation under high temperature conditions such as during molding or other thermal processing. The composition also has a desirable balance of other physical properties.

In certain embodiments, the present invention provides a kit comprising: (i) one or more polycarbonates; (ii) optionally, at least one additional thermoplastic resin different from the polycarbonate; And (iii) at least one rubber-modified thermoplastic resin comprising a discontinuous elastomeric phase dispersed in the hard thermoplastic phase, at least a portion of the hard thermoplastic phase being grafted onto the elastomeric material, wherein the hard thermoplastic phase is one A composition comprising structural units derived from at least one vinyl aromatic monomer, at least one monoethylenically unsaturated nitrile monomer, and at least one monomer selected from (C ₁ -C ₁₂ ) alkyl- and aryl- (meth) acrylate monomers. will be.

In another embodiment, the present invention relates to an article made from said composition and a method of making said composition. Various other features, aspects, and advantages of the invention will become more apparent with reference to the following detailed description and appended claims.

The number of terms in the following specification and claims will be defined to have the following meanings. Singular forms include plural unless specifically indicated otherwise. The term “optional” or “optionally” means that an event or situation described subsequently may or may not occur, and the description includes cases where an event or situation does and does not occur. As used herein, the term “polycarbonate” refers to a polycarbonate comprising structural units derived from carbonate precursors and one or more dihydroxy-substituted aromatic hydrocarbons, and includes copolycarbonates.

Polycarbonates useful in the compositions of the present invention include structural units derived from one or more dihydroxy aromatic hydrocarbons. In various embodiments, structural units derived from one or more dihydroxy aromatic hydrocarbons comprise at least about 60% of the total number of structural units derived from any dihydroxy-substituted hydrocarbons in the polycarbonate, and The remaining structural units derived from hydroxy-substituted hydrocarbons are aliphatic, cycloaliphatic or aromatic radicals.

In an embodiment of the present invention, dihydroxy-substituted aromatic hydrocarbons from which the structural unit of the polycarbonate can be derived include those represented by the following formula (I).

HO --- D --- OH

Where

D is a divalent aromatic radical.

In some embodiments, D has the structure of Formula II:

Where

A ¹ is an aromatic group, including but not limited to phenylene, biphenylene, naphthylenes;

In some embodiments, E comprises methylene, ethylene, ethylidene, propylene, propylidene, isopropylidene, butylene, butylidene, isobutylidene, amylene, amyldene, isoamidene, and the like Alkylene or alkylidene groups, including but not limited to

In some embodiments, when E is an alkylene or alkylidene group, linked by alkylene or alkylidene with other moieties, aromatic linkages, tertiary nitrogen linkages; Ether connector; Carbonyl linkers; Silicon-containing linking groups, including but not limited to silane, siloxy, and the like; Sulfur-containing linkers, including but not limited to sulfides, sulfoxides, sulfones, and the like; And may consist of two or more alkylene or alkylidene groups including, but not limited to, phosphorus-containing linking groups, including but not limited to phosphinyl or phosphonyl, and the like,

In another embodiment, E is cyclopentylidene, cyclohexylidene, 3,3,5-trimethylcyclohexylidene, methylcyclohexylidene, 2- [2.2.1] -bicycloheptylidene, Alicyclic groups including, but not limited to, neopentylidene, cyclopentadedecylidene, cyclododecylidene, adamantylidene, and the like; Sulfur-containing linkers, including but not limited to sulfides, sulfoxides, sulfones, and the like; Phosphorus-containing linking groups, including but not limited to phosphinyl, phosphonyl, and the like; Ether connector; Carbonyl groups; Tertiary nitrogen groups; Silicon-containing linking groups, including but not limited to silane, oxyoxy, and the like;

R ¹ independently in each occurrence comprises a monovalent hydrocarbon group, including but not limited to alkenyl, allyl, alkyl, aryl, aralkyl, alkaryl, cycloalkyl, and the like,

In various embodiments, the monovalent hydrocarbon group of R ¹ can be halogen-substituted, in particular fluoro-substituted, or chloro-substituted, as in dichloroalkylidene, in particular gem-dichloroalkylidene, ;

Y ¹ is independently at each occurrence an inorganic atom, including but not limited to halogen (eg fluorine, bromine, chlorine, iodine); Inorganic groups containing one or more inorganic atoms, including but not limited to nitro; OR ² , wherein R 1 includes, but is not limited to, monovalent hydrocarbon groups including, but not limited to, alkenyl, allyl, alkyl, C ₁ -C ₆ alkyl, aryl, aralkyl, alkaryl, or cycloalkyl ² is a monovalent hydrocarbon group selected from the group consisting of alkyl, aryl, aralkyl, alkaryl or cycloalkyl), but may be an organic group including but not limited to an oxy group,

Only Y ¹ is inert to and should not be affected by the reactants and reaction conditions used to prepare the polymer,

In some specific embodiments, Y ¹ comprises a halo group or a C ₁ -C ₆ alkyl group;

The letter "m" is any integer up to 0 and up to the number of substitutable hydrogens on A ¹ acceptable for substitution;

"p" is any integer greater than or equal to 0 and up to the number of substitutable hydrogens on E that are acceptable for substitution;

"t" is an integer of 1 or more;

"s" is an integer of 0 or 1;

"u" is any integer including 0.

In the dihydroxy-substituted aromatic hydrocarbons in which D is represented by the above formula (II), when one or more Y ¹ substituents are present, they may be the same or different. The same is valid for the R ¹ substituent. When "s" in formula II is "0" and "u" is non-zero, the aromatic ring is directly linked covalently without any intervening alkylidene or other crosslinking. The aromatic nuclear residues hydroxy position of the hydroxyl group and Y ¹ on the A ¹ is ortho, can vary as a meta or para position, when it is substituted with two or more ring carbon atoms Y ¹ and hydroxyl of the hydrocarbon residue boots are close-up, asymmetrical or symmetrical Can exist in relationships. In some specific embodiments, the parameters “t”, “s” and “u” each have a value of 1; All A ¹ radicals are unsubstituted phenylene radicals; E is an alkylidene group such as isopropylidene. In some specific embodiments, all A ¹ radicals are p-phenylene, while all are o- or m-phenylene, or one is o- or m-phenylene and the other may be p-phenylene.

In some embodiments of dihydroxy-substituted aromatic hydrocarbons, E can be an unsaturated alkylidene group. Suitable dihydroxy-substituted aromatic hydrocarbons of this type include those represented by the following general formula (III).

Where

Each R ⁵ is independently hydrogen, chlorine, bromine or a C _1-30 monovalent hydrocarbon or hydrocarbonoxy group,

Z is hydrogen, chlorine or bromine, respectively, and at least one Z is chlorine or bromine.

Suitable dihydroxy-substituted aromatic hydrocarbons also include those represented by the following formula (IV).

Where

Each R ⁴ is independently hydrogen, chlorine, bromine or a C _1-30 monovalent hydrocarbon or hydrocarbonoxy group,

R ^g and R ^h are each independently hydrogen or a C _1-30 hydrocarbon group.

In some embodiments of the invention, the dihydroxy-substituted aromatic hydrocarbons that can be used are described in US Pat. No. 2,991,273, US Pat. No. 2,999,835, US Pat. No. 3,028,365, US Pat. No. 3,148,172, US Pat. And those disclosed by the compound names and formulas (general or special formula) disclosed in US Pat. No. 3,271,367, US Pat. No. 3,271,368, and US Pat. In another embodiment of the invention, the dihydroxy-substituted aromatic hydrocarbons are bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4 -Hydroxyphenyl) sulfoxide, 1,4-dihydroxybenzene, 4,4'-oxydiphenol, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4 '-( 3,3,5-trimethylcyclohexylidene) diphenol; 4,4'-bis (3,5-dimethyl) diphenol, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane; 4,4-bis (4-hydroxyphenyl) heptane; 2,4'-dihydroxydiphenylmethane; Bis (2-hydroxyphenyl) methane; Bis (4-hydroxyphenyl) methane; Bis (4-hydroxy-5-nitrophenyl) methane; Bis (4-hydroxy-2,6-dimethyl-3-methoxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; 1,2-bis (4-hydroxy phenyl) ethane; 1,1-bis (4-hydroxy-2-chlorophenyl) ethane; 2,2-bis (3-phenyl-4-hydroxyphenyl) propane; 2,2-bis (4-hydroxy-3-methylphenyl) propane; 2,2-bis (4-hydroxy-3-ethylphenyl) propane; 2,2-bis (4-hydroxy-3-isopropylphenyl) propane; 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane; 3,5,3 ', 5'-tetrachloro-4,4'-dihydroxyphenyl) propane; Bis (4-hydroxyphenyl) cyclohexyl methane; 2,2-bis (4-hydroxyphenyl) -l-phenylpropane; 2,4'-dihydroxyphenyl sulfone; Dihydroxy naphthalene; 2,6-dihydroxy naphthalene; Hydroquinone; Resorcinol; C _1-3 alkyl substituted resorcinol; Methylresorcinol, catechol; 1,4-dihydroxy-3-methylbenzene; 2,2-bis (4-hydroxyphenyl) butane; 2,2-bis (4-hydroxyphenyl) -2-methylbutane; 1,1-bis (4-hydroxyphenyl) cyclohexane; 4,4'-dihydroxydiphenyl; 2- (3-methyl-4-hydroxyphenyl-2- (4-hydroxyphenyl) propane; 2- (3,5-dimethyl-4-hydroxyphenyl) -2- (4-hydroxyphenyl Propane; 2- (3-methyl-4-hydroxyphenyl) -2- (3,5-dimethyl-4-hydroxyphenyl) propane; bis (3,5-dimethylphenyl-4-hydroxy Phenyl) methane; 1,1-bis (3,5-dimethylphenyl-4-hydroxyphenyl) ethane; 2,2-bis (3,5-dimethylphenyl-4-hydroxyphenyl) propane; 2, 4-bis (3,5-dimethylphenyl-4-hydroxyphenyl) -2-methylbutane; 3,3-bis (3,5-dimethylphenyl-4-hydroxyphenyl) pentane; 1,1- Bis (3,5-dimethylphenyl-4-hydroxyphenyl) cyclopentane; 1,1-bis (3,5-dimethylphenyl-4-hydroxyphenyl) cyclohexane; bis (3,5-dimethylphenyl 4-hydroxyphenyl) sulfoxide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethylphenyl-4-hydroxyphenyl) sulfide, and the like. room In the embodiment, the dihydroxy aromatic hydrocarbon comprises bisphenol-A.

In some embodiments of a dihydroxy-substituted aromatic hydrocarbon in which E of Formula II is an alkylene or alkylidene group, the group can be part of one or more condensed rings linked to one or more aromatic groups comprising one hydroxy substituent. Suitable dihydroxy-substituted aromatic hydrocarbons of this type include compounds of formula V (3- (4-hydroxyphenyl) -1,1,3-trimethylindan-5-ol) and compounds of formula VI: Compound comprising an indene structural unit such as 1- (4-hydroxyphenyl) -1,3,3-trimethylindan-5-ol).

In addition, suitable dihydroxy-substituted aromatic hydrocarbons comprising one or more alkylene or alkylidene groups as part of the condensed ring include 2,2,2 ', 2'-tetrahydro-1,1'- Spirobi [1H-indene] diols.

Where

Each R ⁶ is independently selected from a monovalent hydrocarbon radical and a halogen radical;

R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently C _1-6 alkyl;

R ¹¹ and R ¹² are each independently hydrogen or C _1-6 alkyl;

n is independently an integer of 0-3.

In certain embodiments, 2,2,2 ', 2'-tetrahydro-1,1'-spirobiby [1H-indene] diol is 2,2,2', 2'-tetrahydro-3,3, 3 ', 3'-tetramethyl-1,1'-spirobibi [1H-indene] -6,6'-diol (known as "SBI"). Mixtures comprising any one or more of the hydroxy-substituted hydrocarbons may also be used.

The polycarbonates of the present invention further comprise structural units derived from one or more carbonate precursors. There is no particular limitation on the carbonate precursor. Phosgene or diphenyl carbonate is commonly used. There is no particular limitation on how to prepare suitable polycarbonates. Any known method can be used. In some embodiments, interfacial methods or melt transesterification methods can be used.

In one embodiment of the invention, the polycarbonate comprises one or more homopolycarbonates, wherein the term “homopolycarbonate” refers to a polycarbonate synthesized using only one type of dihydroxy-substituted aromatic hydrocarbon. . In certain embodiments, the polycarbonate comprises bisphenol A homo- or co-polycarbonate, wherein the term "copolycarbonate" refers to one or more types of dihydroxy-substituted hydrocarbons, in particular one or more types of dihydroxy- Reference is made to polycarbonates synthesized using only one type of substituted aromatic hydrocarbon. In another particular embodiment, the polycarbonate comprises a linear homopolycarbonate resin derived from bisphenol A. In other embodiments, the polycarbonate comprises a blend of one or more first polycarbonates with one or more other polymer resins, including, for example, a second polycarbonate different from the first polycarbonate in structural units or molecular weight or in all of these parameters, Or polyesters or additional polymers such as acrylonitrile-styrene-acrylate copolymers.

In various embodiments, the average weight molecular weight of the polycarbonate is about 5,000 to about 200,000. In other specific embodiments, the average weight molecular weight of the polycarbonate is, in one embodiment, from about 10,000 to about 200,000 g / mol, in another embodiment, from about 17,000 to one, as measured by gel permeation chromatography on polystyrene standards. About 100,000 g / mol, in another embodiment about 18,000 to about 80,000 g / mol, in another embodiment about 18,000 to about 40,000 g / mol, in another embodiment about 18,000 to about 36,000 g / mol, another embodiment From about 18,000 to about 30,000 g / mol in embodiments, and from about 18,000 to about 23,000 g / mol in yet another embodiment. In other embodiments, the average weight molecular weight of the polycarbonate is about 28,000 to about 36,000. Suitable polycarbonate resins are, in one embodiment, from about 0.1 to about 1.5 dL / g, in another embodiment from about 0.35 to about 0.9 dL / g, in another embodiment from about 0.4 to about 0.6 when measured in methylene chloride at 25 ° C. Intrinsic viscosity from about 0.48 to about 0.54 dl / g in another embodiment.

In polycarbonate-containing blends, combining one molecular weight grade polycarbonate with a proportion of relatively lower molecular weight grade similar polycarbonate may improve in melt flow and / or other physical properties. Accordingly, the present invention includes compositions comprising only one molecular weight grade polycarbonate, and also compositions comprising two or more molecular weight grade polycarbonates. When two or more molecular weight grade polycarbonates are present, the weight average molecular weight of the lowest molecular weight polycarbonate is from about 10 to about 95% in one embodiment, and in another embodiment about the weight average molecular weight of the highest molecular weight polycarbonate 40 to about 85%, and in another embodiment about 60 to about 80%. In an exemplary embodiment, the polycarbonate-containing blends of non-limiting embodiments include those comprising polycarbonates having a weight average molecular weight of about 18,000 to about 23,000 in combination with polycarbonates having a weight average molecular weight of about 28,000 to about 36,000 (in all cases polystyrene Based on standards). When two or more molecular weight grade polycarbonates are present, the weight ratio of the various molecular weight grades may be from about 1 to about 99 parts of one molecular weight grade and from about 99 to about 1 part of any other molecular weight grade. In some embodiments, a mixture of two molecular weight grade polycarbonates is used, in which case the weight ratio of the two grades is in one embodiment from about 99: 1 to about 1:99, in another embodiment from about 80:20 to about 20:80, in another embodiment from about 70:30 to about 30:70. Because not all manufacturing methods for preparing polycarbonates can make all molecular weight grades constituted, the present invention includes compositions comprising two or more molecular weight grade polycarbonates, each of which is produced by a different manufacturing method. do. In one particular embodiment, the present invention includes compositions comprising polycarbonates produced by the interfacial method together with polycarbonates of different weight average molecular weights produced by the melting method.

The amount of polycarbonate present in the composition of the present invention is from about 5 to about 95 weight percent in one embodiment, from about 20 to about 85 weight percent in another embodiment, about 25 in another embodiment based on the weight of the total composition To about 80% by weight.

In various embodiments, the composition of the present invention comprises a rubber-modified thermoplastic resin comprising a discontinuous elastomeric phase and a hard thermoplastic phase, wherein at least a portion of the hard thermoplastic phase is grafted onto the elastomer. The composition is derived by grafting one or more rubber substrates. The rubber substrate comprises a discontinuous elastomeric phase of the composition. There is no particular limitation on the rubber substrate, but it may be easy to be grafted by at least a portion of the graftable monomer. The rubber substrate typically has a glass transition temperature (Tg) of less than about 0 ° C. in one embodiment, less than about −20 ° C. in another embodiment, and less than about −30 ° C. in another embodiment.

In various embodiments, the rubber substrate is capable of forming one or more monoethylenically unsaturated alkyl (meth) acrylate monomers selected from (C ₁ -C ₁₂ ) alkyl (meth) acrylate monomers and one or more of the monomers by known methods. It is derived from the polymerization of the mixture comprising. As used herein, the term "monoethylenic unsaturation" means having a single site of ethylenic unsaturation per molecule, and the term "(meth) acrylate monomer" collectively refers to acrylate monomers and methacrylate monomers. Refers to. As used herein, the term "(C _x -C _y )" applied to certain units, such as compounds or chemical substituents, refers to those having a carbon atom content of "x" carbon atoms to "y" carbon atoms per such unit. it means. For example, "(C ₁ -C ₁₂ ) alkyl" means a straight, branched or cyclic alkyl substituent having 1 to 12 carbon atoms per group, methyl, ethyl, n-propyl, isopropyl, n-butyl , s-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl. Suitable (C ₁ -C ₁₂ ) alkyl (meth) acrylate monomers include, by way of example, ethyl acrylate, butyl acrylate, iso-pentyl acrylate, n-hexyl acrylate and 2-ethyl hexyl acrylate ₁ -C ₁₂ ) alkyl acrylate monomers; And as an illustrative example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, iso-propyl methacrylate, butyl meth his (C ₁ -C contained an acrylate, hexyl methacrylate, and decyl methacrylate ₁₂ ) alkyl methacrylate analogs, including but not limited to. In certain embodiments of the invention, the rubber substrate comprises structural units derived from n-butyl acrylate.

In various embodiments, the rubber substrate can also include structural units derived from one or more polyethyleneic unsaturated monomers. As used herein, the term "polyethylenic unsaturation" means having two or more sites of ethylenic unsaturation per molecule. Polyethylenically unsaturated monomers are often used to provide crosslinking of rubber particles and to provide "graftlinking" sites in the rubber substrate for subsequent reaction while grafting the monomers. Suitable polyethyleneic unsaturated monomers include butylene diacrylate, divinyl benzene, butene diol dimethacrylate, trimethylolpropane tri (meth) acrylate, allyl methacrylate, diallyl methacrylate, diallyl male 8, diallyl fumarate, diallyl phthalate, triallyl methacrylate, triallyl isocyanurate, triallyl cyanurate, acrylate of tricyclodecenyl alcohol, and mixtures comprising one or more of the above monomers Including but not limited to. In certain embodiments, the rubber substrate comprises structural units derived from triallyl cyanurate.

In some embodiments, the rubber substrate may optionally include structural units derived from small amounts of other unsaturated monomers, examples of which may be copolymerized with allyl (meth) acrylate monomers used to prepare the rubber substrate. Suitable copolymerizable monomers include C ₁ -C ₁₂ aryl or haloaryl substituted acrylates, C ₁ -C ₁₂ aryl or haloaryl substituted methacrylates, or mixtures thereof; Monoethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid and itaconic acid; Glacidyl (meth) acrylate, hydroxy alkyl (meth) acrylate, hydroxy (C ₁ -C ₁₂ ) alkyl (meth) acrylates such as hydroxyethyl methacrylate, (C ₄ -C ₁₂ ) cyclo Alkyl (meth) acrylate monomers such as cyclohexyl methacrylate; (Meth) acrylamide monomers such as acrylamide, methacrylamide and N-substituted acrylamide or -methacrylamide; Maleimide monomers such as maleimide, N-alkyl maleimide, N-aryl maleimide and haloaryl substituted maleimide; Maleic anhydride; Vinyl methyl ethers, vinyl esters such as vinyl acetate and vinyl propionate. As used herein, the term "(meth) acrylamide" refers collectively to acrylamide and methacrylamide. Suitable copolymerizable monomers also include vinyl aromatic monomers such as styrene with one or more alkyl, alkoxy, hydroxy or halo substituents attached to the aromatic ring and substituted styrenes such as alkoxy-methyl styrene, p-methyl styrene , 3,5-diethylstyrene, 4-n-propylstyrene, vinyl toluene, alpha-methyl vinyltoluene, vinyl xylene, trimethyl styrene, butyl styrene, t-butyl styrene, chlorostyrene, Alpha-chlorostyrene, dichlorostyrene, tetrachlorostyrene, bromostyrene, alpha-bromostyrene, dibromosstyrene, p-hydroxystyrene, p-acetoxystyrene, methoxystyrene Lene and vinyl-substituted condensed aromatic ring structures such as vinyl naphthalene, vinyl atracene, and vinyl aromatic monomers with monoethylenically unsaturated nitrile monomers. Mixture, such as a nitrile, acrylic eth- as acrylonitrile, meth acrylonitrile, alpha-bromo acrylic nitrile and alpha-chloro-acrylic contains a nitro reel, but are not limited to: Also suitable are substituted styrenes having a mixture of substituents on the aromatic ring.

The rubber substrate is about 10 to about 94 weight percent in one embodiment, about 10 to about 80 weight percent in another embodiment, based on the weight of the rubber modified thermoplastic resin in the rubber modified thermoplastic portion of the composition of the present invention, About 15 to about 80 weight percent in other embodiments, about 35 to about 80 weight percent in other embodiments, about 40 to about 80 weight percent in other embodiments, about 25 to about 60 weight percent in other embodiments, another In embodiments, it may be present at a level of about 40 to about 50% by weight. In other embodiments, the rubber substrate is from about 5 to about 50 weight percent, from about 8 to about 40 weight percent, or from about 10 to about 50 weight percent, based on the weight of the rubber modified thermoplastic resin in the rubber modified thermoplastic portion of the composition of the present invention. It may be present at a level of about 30% by weight.

There is no particular limitation on the particle size distribution of the rubber substrate (hereafter referred to herein as the initial rubber substrate, which is often distinguished from the rubber substrate according to grafting). In some embodiments, the rubber substrate may have a broadband particle size distribution with particles of about 50 to about 1000 nm in size. In other embodiments, the number average particle size of the rubber substrate may be less than about 100 nm. In yet another embodiment, the number average particle size of the rubber substrate can be about 80 to about 500 nm. In yet another embodiment, the number average particle size of the rubber substrate can be about 200 to about 750 nm. In other embodiments, the number average particle size of the rubber substrate may be greater than about 400 nm.

In order to produce the rubber modified thermoplastic resins used in the present invention, the monomers polymerize in the presence of a rubber substrate, thereby forming a graft copolymer, at least some of which are chemically grafted onto the rubber. Any portion of the graft copolymer that is not chemically grafted to the rubber substrate comprises a hard thermoplastic phase. The hard thermoplastic phase comprises a thermoplastic polymer or copolymer exhibiting a glass transition temperature (Tg) of greater than about 25 ° C. in one embodiment, at least 90 ° C. in another embodiment, and at least 100 ° C. in another embodiment.

In certain embodiments, the hard thermoplastic phase of the rubber-modified thermoplastic resin comprises one or more vinyl aromatic monomers, one or more monoethylenically unsaturated nitrile monomers, and (C ₁ -C ₁₂ ) alkyl- and aryl- (meth) acrylates. Structural units derived from one or more monomers selected from the group consisting of monomers. Suitable (C ₁ -C ₁₂ ) alkyl- and aryl- (meth) acrylate monomers, vinyl aromatic monomers and monoethylenically unsaturated nitrile monomers include those as previously disclosed herein in the description of the rubber substrate. In certain embodiments, the hard thermoplastic phase comprises a first structural unit derived from one or more vinyl aromatic monomers, a second structural unit derived from one or more monoethylenically unsaturated nitrile monomers, and (C ₁ -C ₁₂ ) alkyl- and aryl Vinyl aromatic polymers comprising a third structural unit derived from at least one monomer selected from the group consisting of-(meth) acrylate monomers. Suitable vinyl aromatic polymers comprise at least about 20% by weight of structural units derived from one or more vinyl aromatic monomers. Examples of such vinyl aromatic polymers are styrene / acrylonitrile / methyl methacrylate copolymer, alpha-methyl styrene / acrylonitrile / methyl methacrylate copolymer and styrene / alpha-methyl styrene / acrylic Ronitrile / methyl methacrylate copolymers include, but are not limited to. These copolymers can be used individually or in mixed form on hard thermoplastic phases.

When the structural unit in the copolymer is derived from one or more monoethylenically unsaturated nitrile monomers, the nitrile monomer content in the copolymer comprising the graft copolymer and the hard thermoplastic phase is determined in the air including the graft copolymer and the hard thermoplastic phase. From about 5 to about 40 weight percent in one embodiment, about 5 to about 30 weight percent in another embodiment, about 10 to about 30 weight percent in another embodiment, about 15 in another embodiment To about 30% by weight.

The amount of grafting that occurs between the rubber phase and the monomer comprising the hard thermoplastic phase of the rubber-modified thermoplastic is varied by the relative amount and composition of the rubber phase. In one embodiment, more than about 10 weight percent of the hard thermoplastic phase is chemically grafted to the rubber based on the total amount of the hard thermoplastic phase in the composition. In another embodiment, more than about 15 weight percent of the hard thermoplastic phase is chemically grafted to the rubber based on the total amount of the hard thermoplastic phase in the composition. In another embodiment, more than about 20 weight percent of the hard thermoplastic phase is chemically grafted to the rubber based on the total amount of the hard thermoplastic phase in the composition. In certain embodiments, the amount of hard thermoplastic phase chemically grafted to the rubber is about 5 to about 90 weight percent, about 10 to about 90 weight percent, about 15 to about 85 weight percent, about based on the total amount of hard thermoplastic phase in the composition 15 to about 50 weight percent, or about 20 to about 50 weight percent. In another embodiment, about 40-90 weight percent of the hard thermoplastic phase is free. That is, it is not grafted.

The hard thermoplastic phase of the rubber-modified thermoplastic resin is about 85 to about 6 weight percent in one embodiment, about 65 to about 6 weight percent in other embodiments, and in other embodiments about the rubber-modified thermoplastic resin by weight. 60 to about 20 weight percent, in another embodiment about 75 to about 40 weight percent, and in another embodiment about 60 to about 50 weight percent. In other embodiments, the hard thermoplastic phase can be present from about 90 to about 30 weight percent based on the weight of the rubber-modified thermoplastic resin.

The hard thermoplastic phase of the rubber-modified thermoplastic is formed alone by polymerization carried out in the presence of a rubber substrate, or one or more separate polymerized hard thermoplastic polymers are added to the hard thermoplastic polymer polymerized in the presence of a rubber substrate. Can be formed. When at least a portion of the separately synthesized hard thermoplastic phase is added to the composition, the amount of the separately synthesized hard thermoplastic phase added is present in an amount of about 30 to about 80 weight percent based on the weight of the rubber-modified thermoplastic resin. Two or more different rubber substrates having different number average particle sizes can be used separately in this polymerization reaction, after which the products can be blended together. In an exemplary embodiment in which these products, each having a different number average particle size of the initial rubber substrate, are blended together, the ratio of the substrates is from about 90:10 to about 10:90, from about 80:20 to about 20:80, Or about 70:30 to about 30:70. In some embodiments, the initial rubber substrate having a smaller particle size is the major component in such blends containing one or more particle sizes of the initial rubber substrate.

Hard thermoplastic phases of rubber-modified thermoplastics can be prepared according to known methods, such as bulk polymerization, emulsion polymerization, suspension polymerization or combinations thereof, wherein at least a portion of the hard thermoplastic phase is combined with the unsaturated sites present in the rubber phase. Through the reaction, they are chemically bonded, ie "grafted" on the rubber. The grafting reaction can be carried out in a batch, continuous or semicontinuous manner. Exemplary procedures include, but are not limited to, those taught in US Pat. No. 3,944,631, and US patent application Ser. No. 08 / 962,458, filed October 31,1997. Unsaturation sites in the rubber phase are provided by residual unsaturated sites in the structural units of the rubber, for example derived from grafting link monomers.

In some embodiments of the invention, rubber-modified thermoplastics are prepared by a process comprising grafting a monomer to a rubber substrate with simultaneous formation of a hard thermoplastic phase, the process comprising at least one first monomer After grafting to the substrate, grafting of at least one second monomer different from the first monomer is carried out. Here, the change from one grafting step to the next is defined as the point where there is a change in the identity of one or more monomers added to the rubber substrate for grafting. In one embodiment of the present invention, the formation of the hard thermoplastic phase and the grafting on the rubber substrate are carried out over time by supplying at least one first monomer to the reaction mixture comprising the rubber substrate. Here, the second grafting step occurs when one or more different monomers are introduced into the feed stream in the presence or absence of one or more first monomers.

Two or more steps are used for the grafting, but additional steps may also be used. The first grafting step is carried out using at least one monomer comprising a vinyl aromatic monomer, a monoethylenically unsaturated nitrile monomer, and optionally (C ₁ -C ₁₂ ) alkyl- and aryl- (meth) acrylate monomers. do. In certain embodiments, the grafting is performed in a first step using a mixture of monomers wherein at least one is selected from the group consisting of vinyl aromatic monomers and at least one is selected from the group consisting of monoethylenically unsaturated nitrile monomers. When a mixture comprising at least one vinyl aromatic monomer and at least one monoethylenically unsaturated nitrile monomer is used in the first grafting step, the weight / weight ratio of the vinyl aromatic monomer to the monoethylenically unsaturated nitrile monomer is one implementation. From about 1: 1 to about 6: 1 in another embodiment, from about 1.5: 1 to about 4: 1 in another embodiment, from about 2: 1 to about 3: 1 in another embodiment, about 2.5: 1 in another embodiment To about 3: 1, in another embodiment about 2.5: 1 to about 3: 1. In a preferred embodiment, the weight / weight ratio of the vinyl aromatic monomer to monoethylenically unsaturated nitrile monomer used in the first grafting step is about 2.6: 1.

In one or more subsequent steps after the first step, the grafting comprises a vinyl aromatic monomer, a monoethylenically unsaturated nitrile monomer, and optionally a (C ₁ -C ₁₂ ) alkyl- and aryl- (meth) acrylate monomer. It is carried out using one or more monomers comprising. In certain embodiments, the grafting is carried out in one or more subsequent steps using one or more monomers, wherein at least one is selected from the group consisting of (C ₁ -C ₁₂ ) alkyl- and aryl- (meth) acrylate monomers. In another particular embodiment, the grafting is at least one selected from the group consisting of (C ₁ -C ₁₂ ) alkyl- and aryl- (meth) acrylate monomers and at least one vinyl aromatic monomer and monoethylenically unsaturated nitrile It is carried out in one or more subsequent steps using a mixture of monomers selected from the group consisting of monomers. In other particular embodiments, the grafting is selected from the group consisting of one or more (C ₁ -C ₁₂ ) alkyl- and aryl- (meth) acrylate monomers; At least one is selected from the group consisting of vinyl aromatic monomers and at least one is carried out in at least one subsequent step using a mixture of monomers selected from the group consisting of monoethylenically unsaturated nitrile monomers. The (C ₁ -C ₁₂ ) alkyl- and aryl- (meth) acrylate monomers, vinyl aromatic monomers and monoethylenically unsaturated nitrile monomers include those described herein above.

In the first grafting step, the total amount of monomers used for grafting to the rubber substrate is about 5 to about 98 weight percent in one embodiment, based on the total amount of monomers used for grafting in all steps, another embodiment About 5 to about 95 weight percent in embodiments, about 10 to about 90 weight percent in other embodiments, about 15 to about 85 weight percent in other embodiments, about 20 to about 80 weight percent in other embodiments, another embodiment About 30 to about 70% by weight. In certain embodiments, the total amount of monomers used for grafting to the rubber substrate in the first step is about 30 to about 95 weight percent based on the total amount of monomers used for grafting in all steps. Then, in at least one step after the first step, further monomers are grafted to the rubber substrate. In certain embodiments, all further monomers are grafted to the rubber substrate in one second step after the first step.

One or more (C ₁ -C ₁₂ ) alkyl- and aryl- (meth in a first step or a second step of grafting the monomer to the rubber substrate, or for grafting to the rubber substrate in the first and second steps ) Acrylate monomers are used. The total amount of the (meth) acrylate monomers used is from about 95 to about 2 weight percent in one embodiment, from about 80 to about 2 weight percent in another embodiment based on the total amount of all monomers used for grafting From about 70 to about 2 weight percent in embodiments, from about 50 to about 2 weight percent in other embodiments, from about 45 to about 2 weight percent in other embodiments, from about 45 to about 5 weight percent in another embodiment. In another embodiment of the present invention, the total amount of the (meth) acrylate monomers used is about 48 to about 18 weight percent.

In a mixture of monomers comprising one or more (C ₁ -C ₁₂ ) alkyl- and aryl- (meth) acrylate monomers, the (meth) acrylate monomers vs. other used for grafting to the rubber substrate in any particular step The weight / weight ratio of the sum of the monomers is from about 10: 1 to about 1:10 in one embodiment, from about 8: 1 to about 1: 8 in other embodiments, from about 5: 1 to about 1: 5 in another embodiment. , From about 4: 1 to about 1: 4 in other embodiments, from about 3: 1 to about 1: 3 in other embodiments, from about 2: 1 to about 1: 2 in other embodiments, about 1.5 in another embodiment : 1 to about 1: 1.5.

Optionally, one or more additional thermoplastic resins different from the polycarbonate may be present in the compositions of the present invention. Exemplary further thermoplastics include (meth) acrylate homopolymers and copolymers, methyl methacrylate-butyl acrylate copolymers, methyl methacrylate-ethyl acrylate copolymers, styrene and alkylstyrene homopolymers and copolymers Copolymer, styrene-acrylonitrile (SAN) copolymer, alpha-methylstyrene-acrylonitrile (AMSAN) copolymer, methyl methacrylate-styrene-acrylonitrile (MMA-SAN) terpolymer Copolymers, methylmethacrylate / alpha-methylstyrene / acrylonitrile (MMA-AMSAN) terpolymers and mixtures thereof. In some embodiments, the additional thermoplastic resin different from the polycarbonate is present the same as or in addition to the separately polymerized rigid thermoplastic polymers mentioned herein above. When present, the additional thermoplastic resin is present in the composition at about 1 to about 80 weight percent, about 20 to about 70 weight percent, and about 25 to about 60 weight percent based on the weight of the total composition.

Compositions of the present invention may optionally contain stabilizers such as color stabilizers, heat stabilizers, light stabilizers, antioxidants and UV stabilizers; corrector; Flame retardants, anti-drip agents, lubricants, flow promoters and other processing aids; Plasticizers, antistatic agents, mold release agents, impact modifiers, fillers, and colorants such as dyes and pigments, which may be organic, inorganic or organometallic; And similar additives, including but not limited to conventional additives known in the art. Exemplary additives include silica, silicates, zeolites, titanium dioxide, stone powder, glass fibers or spheres, carbon fibers, carbon black, conductive carbon black, graphite, calcium carbonate, talc, mica, Lithopone, zinc oxide, zirconium silicate, iron oxide, diatomaceous earth, calcium carbonate, magnesium oxide, chromium oxide, zirconium oxide, aluminum oxide, crushed quartz, clay, calcined clay , Organoclay, talc, kaolin, asbestos, cellulose, wood flour, cork, cotton and synthetic textile fibers, reinforcing fillers, glass fibers, carbon fibers, conductive carbon fibers, carbon nanotubes ), And metal fibers. Often, one or more additives are included in the compositions of the present invention, and in some embodiments one or more types of additives are included. In certain embodiments, the composition further comprises an additive selected from the group consisting of colorants, dyes, pigments, lubricants, mold release agents, stabilizers, fillers, and mixtures thereof.

In another embodiment, the present invention includes a method of making a composition disclosed herein. The composition can be prepared by combining the components of the composition and intimately mixing them under conditions suitable to form a blend of components, examples of which include, for example, two-roll mills, kneaders, Benbury Melt mixing using a mixer, disc-pack processor, single screw extruder or co-rotating or counter-rotating twin screw extruder, and then the composition thus formed such as pelleting the composition Including but not limited to reducing to particulate form by quenching or polishing. Due to the admissibility of melt blending equipment in commercial polymer processing facilities, melt processing procedures are generally preferred. If the compositions are prepared by extrusion, they can be prepared by adjusting the addition of the various components at various points in the mixing process using a single extruder having multiple feed ports along its length. In addition, it is sometimes advantageous to use one or more vent ports in each section between the feed ports to allow venting of the melt (atmospheric pressure or vacuum). Those skilled in the art will be able to adjust the blending time and temperature as well as the location and order of ingredient additions without inappropriate additional experimentation.

The composition of the present invention may be formed into a useful article. In some embodiments, the article is a unitary article comprising the composition of the present invention. In other embodiments, the articles can comprise a multilayer article comprising one or more layers comprising a composition of the present invention.

Multilayer and single articles that can be prepared, including compositions made by the methods of the present invention, include articles for the field of outdoor vehicle and device (OVAD); Aircraft, automobiles, trucks, military vehicles (including cars, aircraft and water-borne vehicles), scooters, and motorcycles such as panels, quarter panels, rockers Panels, vertical panels, horizontal panels, trims, columns, center posts, fenders, doors, rear deck, trunks, hoods, bonnets, roofs, bumpers, instrument panels ( fascia, grille, mirror housing, pillar applique, cladding, body side molding, wheel cover, wheelcap, door handle, spoiler, window frame, headlight bezel bezels and external and internal components for housings, taillight housings, taillight bezels, license plate enclosures, roof racks, and running boards; Enclosures, housings, panels, and components for outdoor vehicles and devices; Enclosures for electrical and communication devices; Outdoor furniture; Aircraft components; Boat and marine equipment, including trims, enclosures, and housings; Outboard motor housings; Depth finder housings, personal water-crafts; Jet ski; swimming pool; Spa; Hot tubs; stairs; Step covering; Building and construction applications such as window panes, fencing, decking planks, roofs; Siding, in particular vinyl siding use; Windows, floors, decorative window furniture or treatments; Wall panels and doors; Outdoor and indoor signs; Enclosures, housings, panels, and components for automated teller machines (ATMs); Enclosures, housings, panels and parts for lawn and garden tractors, lawn mowers and tools, including lawn and garden tools; Window and door trim; Sports equipment and ornaments; Enclosures, housings, panels and parts for snowmobiles; Recreational vehicle panels and components; Playground equipment; Articles made from plastic-wood combinations; Golf course markers; A utility pit cover; Mobile phone housings; Radio transmitter housings; Radio receiver housings; Optical equipment; Optical switch; Electrical sockets; Lighting fixtures; Reflector; A network interface device housing; Transformer housing; Air conditioning housing; Cladding or seats for public transport; Cladding or seats for trains, subways or buses; Instrument housing; An antenna housing; Cladding for satellite dish; And similar uses. Such articles include, but are not limited to, profile extrusion, sheet extrusion, coextrusion, extrusion injection molding, thermoforming, injection molding, compression molding, in-mold decoration, baking in paint ovens, plating and lamination. Can be prepared by various known processes and fabrication steps.

Without further deliberation, it is believed that one skilled in the art can, using the present disclosure, utilize the present invention to its fullest extent. The following examples are included to provide further guidance in practicing the claimed invention to those skilled in the art. The examples provided are only representative of the research contributing to the teachings of the present invention. Accordingly, these examples are not intended to limit the invention in any way as defined in the appended claims.

In the examples below, Vicat B data at 120 ° C. was measured according to ISO 306. Flex plate impact strength was measured according to ISO 6603/2. Notched Izod impact strength was measured according to ISO 180 / 1A. The oil volume fraction (MVR) at 260 ° C. was measured on the granulate using a 5 kg weight according to ISO 1133.

Examples 1-5

As described in US patent application Ser. No. 10 / 748,394, filed Dec. 30, 2003, this example illustrates the preparation of a rubber-modified thermoplastic resin by staged supply of monomers for grafting. The shaken reaction mixture comprising 212.8 parts of deionized water and 45 parts of PBA in the broad particle size distribution was heated to 60 ° C. Various amounts of monomer mixture consisting of styrene and acrylonitrile (2: 1 weight / weight ratio) are fed to the respective reactions in the first step, while styrene, acrylonitrile and methyl ketacrylate (40 A variable amount of monomer mixture consisting of: 25: 35 weight / weight / weight ratio) was fed to each reaction in the second step. The monomer feed times were adjusted according to the relative amount of monomer fed so that the total monomer flow rate remained constant at 55 parts of total monomer added continuously over 90 minutes. In addition, an activator solution of 0.225 parts of gumen hydroperoxide and 5 parts of deionized water, 0.0033 parts of ferric sulfate heptahydrate, 0.3 parts of sodium formaldehyde sulfoxylate, and 0.0165 parts of disodium salt of ethylene diamine tetraacetic acid over 125 minutes It was fed continuously to each reaction mixture. The final product comprising the hard thermoplastic phase and the grafted rubber substrate was coagulated with aqueous calcium chloride and dried in a fluid bed drier at 70 ° C. Table 1 below shows the weight parts (pbw) of monomers fed to each reaction mixture. All values for the weight percent gel represent the acetone-insoluble portion of the product, which typically includes PBA and any additional monomer species grafted to the PBA.

Examples 6-9

The production of rubber-modified thermoplastics by the stepwise supply of monomers for grafting, under similar conditions as described in Examples 1-5 above, 45 parts by weight of poly (butyl acrylate) (PBA) rubber substrates in various% It proceeded by grafting in two steps with 55 parts by weight of a monomer mixture comprising styrene-acrylonitrile-methyl methacrylate in a ratio (weight / weight / weight, total 100). The rubber substrate in each case was prepared by a continuous procedure and consisted of a wide range of rubber particle size distributions. Table 2 below shows the amounts of styrene, acrylonitrile and methyl methacrylate used in each grafting reaction in each step, and characteristic data for the resulting product.

Example 10

The preparation of the rubber-modified thermoplastic resin was carried out under conditions similar to those of Example 9, except that 45 parts of PBA having a number average particle size of 475 nm were used. In addition, dimer fatty acid surfactants were used and the final product comprising the hard thermoplastic phase and the grafted rubber substrate was coagulated with sulfuric acid.

Example 11

Preparation of the rubber-modified thermoplastic resin was carried out under conditions similar to those of Example 9 except that 45 parts of PBA having a number average particle size of 90 nm were used. In addition, dimer fatty acid surfactants were used and the final product comprising the hard thermoplastic phase and the grafted rubber substrate was coagulated with sulfuric acid.

Example 12

The preparation of the rubber-modified thermoplastic resin was carried out under conditions similar to those of Example 9, except that 45 parts of PBA having a number average particle size of 475 nm were used. In addition, a sodium lauryl sulfate surfactant was used (e.g., using a method similar to that described in European Patent Application EP 0913408) and the final product comprising the hard thermoplastic phase and the grafted rubber substrate was solidified with calcium chloride. .

Example 13

Preparation of the rubber-modified thermoplastic resin was carried out under conditions similar to those of Example 9 except that 45 parts of PBA having a number average particle size of 90 nm were used. In addition, using sodium lauryl sulfate surfactant, the final product comprising the hard thermoplastic phase and the grafted rubber substrate was solidified with calcium chloride.

Example 14

The production of rubber-modified thermoplastics by the stepwise supply of monomers for grafting comprises 45 parts by weight of poly (butyl acrylate) (PBA) rubber substrate in various% ratios (weight / weight / weight, total 100). It proceeded by grafting in two steps with 55 parts by weight of a monomer mixture comprising len-acrylonitrile-methyl methacrylate. Rubber substrates were prepared by a continuous procedure and consisted of a wide range of rubber particle size distributions. In the first step, the rubber was grafted to 22.69 pbw styrene and 7.56 pbw acrylonitrile. In a second step, the rubber was grafted with 9.9 pbw of styrene, 3.71 pbw of acrylonitrile and 11.14 pbw of methyl methacrylate. Rubber-modified thermoplastics were obtained.

Examples 15-20

The production of rubber-modified thermoplastics by the stepwise supply of monomers for grafting, under similar conditions as described in Examples 1-5 above, 45 parts by weight of poly (butyl acrylate) (PBA) rubber substrates in various% It proceeded by grafting in two steps with 55 parts by weight of a monomer mixture comprising styrene-acrylonitrile-methyl methacrylate in a ratio (weight / weight / weight, total 100). The PBA used was a blend of 100 nm average particle size PBA with a 70:30 ratio and PBA of 500 nm average particle size. Table 3 below shows the amounts of styrene, acrylonitrile and methyl methacrylate used in each grafting reaction in each step.

Examples 21-25 and Comparative Examples

Bisphenol A polycarbonate (33 parts by weight with a weight average molecular weight of about 28,000 to about 36,000 g / mol relative to the polystyrene standard)) and suspension-prepared (derived from 75% styrene and 25% acrylonitrile) A composition comprising 40 parts by weight of SAN was combined with 27 parts by weight of various rubber-modified thermoplastics by the stepwise supply of monomers for grafting. In addition, all compositions comprise 4 parts by weight of copolymers derived from methyl methacrylate and butyl acrylate; 1.28 parts by weight of mold release agent, heat stabilizer and UV blocker; 12 parts by weight of coated titanium dioxide; And 0.1 parts by weight of other pigments. The composition in this example was prepared by dry blending the components in a mixer and then extruding using typical processing equipment at about 200-250 ° C. The extrudate was pelleted, dried and molded at various melt temperatures. Table 4 below shows a variety of rubber-modified thermoplastics prepared by the stepwise feeding of styrene, acrylonitrile and methyl methacrylate monomers for grafting (referred to as M-ASA-grafting). In another embodiment, except using a rubber-modified thermoplastic resin (referred to as ASA) prepared by grafting 45 pbw of poly (butyl acrylate) to 36.5 pbw of styrene and 19 pbw of acrylonitrile in a single step Comparative Example (C.Ex.) having the same composition as was prepared. Test specimens were molded at 255 ° C. melt temperature and further molded at 300 ° C. melt temperature to stimulate abusive conditions. Molded test specimens were color measured in a CIE L ^* a ^* b ^* space using a MacBeth 7000 spectrometer for color measurements. The values for delta E representing the color difference between the samples molded at 225 ° C. and 300 ° C. are shown in Table 4 below. In addition, selected physical properties for test specimens molded at 255 ° C. (unless otherwise indicated) are presented in Table 4 below.

* Measured on the part molded at 300 ° C.

The data indicate that a composition containing a rubber-modified thermoplastic resin comprising structural units derived from methyl methacrylate contains a rubber-modified thermoplastic resin prepared without structural units derived from methyl methacrylate. It is suggested to have the color characteristics and gloss at the time of exposure to the elevated temperature compared with what is shown by.

Examples 26-29 and Comparative Examples

Compositions were prepared as described in Examples 21-25 using similar amounts of ingredients. Table 5 below shows a variety of rubber-modified thermoplastics prepared by the staged feeding of styrene, acrylonitrile and methyl methacrylate monomers for grafting (referred to as M-ASA-grafting). In another embodiment, except using a rubber-modified thermoplastic resin (referred to as ASA) prepared by grafting 45 pbw of poly (butyl acrylate) to 36.5 pbw of styrene and 19 pbw of acrylonitrile in a single step Comparative Example (C.Ex.) having the same composition as was prepared. Test specimens were molded at 255 ° C. melt temperature and further molded at 300 ° C. melt temperature to stimulate poor conditions. Molded test specimens were color measured in a CIE L ^* a ^* b ^* space using a MacBeth 7000 spectrometer for color measurements. The values for delta E representing the color difference between the samples molded at 225 ° C. and 300 ° C. are shown in Table 5 below. In addition, selected physical properties for test specimens molded at 255 ° C. (unless otherwise indicated) are presented in Table 5 below.

* Measured on the part molded at 300 ° C.

The data indicate that a composition containing a rubber-modified thermoplastic resin comprising structural units derived from methyl methacrylate contains a rubber-modified thermoplastic resin prepared without structural units derived from methyl methacrylate. It is suggested to have the color characteristics and gloss at the time of exposure to the elevated temperature compared with what is shown by.

Examples 30 to 32 and Comparative Examples

40 parts by weight of various thermoplastic resins were added instead of 40 parts by weight of suspension-manufactured SAN derived from 75% styrene and 25% acrylonitrile, using similar amounts of components as described in Examples 15-19. The composition was prepared as follows. The various thermoplastic resins include terpolymers (named “MMA-SAN”) derived from 40% styrene, 25% acrylonitrile and 35% methyl methacrylate; Copolymers derived from 30% alpha-methyl styrene and 70% acrylonitrile (named “AMSAN”); And copolymers derived from 66% styrene and 34% acrylonitrile (named "SAN 66:33"). Each composition included 27 parts by weight of the rubber-modified thermoplastic resin of Example 9. Table 6 below shows the properties of the added thermoplastic resin. Rubber-modified thermoplastics (referred to as ASA) prepared by grafting 45 pbw of poly (butyl acrylate) to 36.5 pbw of styrene and 19 pbw of acrylonitrile in a single step, and suspension-produced SAN (75% sty) A comparative example (C.Ex.) was prepared having the same composition as in the other examples, except that it was derived from lene and 25% acrylonitrile and named "SAN 75:25". Test specimens were molded at 255 ° C. melt temperature and further molded at 300 ° C. melt temperature to stimulate poor conditions. Molded test specimens were color measured in a CIE L ^* a ^* b ^* space using a MacBeth 7000 spectrometer for color measurements. The values for delta E representing the color difference between the samples molded at 225 ° C. and 300 ° C. are shown in Table 6 below. In addition, selected physical properties for test specimens molded at 255 ° C. (unless otherwise indicated) are presented in Table 6 below.

* Measured on the part molded at 300 ° C.

The data indicate that a composition containing a rubber-modified thermoplastic resin comprising structural units derived from methyl methacrylate contains a rubber-modified thermoplastic resin prepared without structural units derived from methyl methacrylate. It is suggested to have the color characteristics and gloss at the time of exposure to the elevated temperature compared with what is shown by.

Example 33 and Comparative Example

A composition comprising the following components was prepared: 18 pbw of bisphenol A polycarbonate having a weight average molecular weight of about 18,000 to about 23,000 g / mol relative to the polystyrene standard; 42 pbw of bisphenol A polycarbonate having a weight average molecular weight of about 28,000 to about 36,000 g / mol relative to the polystyrene standard; And 2 parts by weight of suspension-prepared SAN (derived from 75% styrene and 25% acrylonitrile). The composition further included 18 parts by weight of rubber-modified thermoplastic resin prepared as in Example 9. In addition, the composition is 0.5 part by weight of a mold release agent and a heat stabilizer; 12 parts by weight of coated titanium dioxide; And 0.1 parts by weight of other pigments. The composition in this example was prepared by dry blending the components in a mixer and then extruding using typical processing equipment. The extrudate was pelleted, dried and molded. Having the same composition, except using a rubber-modified thermoplastic resin (referred to as ASA) prepared by grafting 45 pbw of poly (butyl acrylate) to 36.5 pbw of styrene and 19 pbw of acrylonitrile in a single step Comparative Example (C.Ex.) was prepared. Test specimens were molded at 260 ° C. melt temperature and further molded at 320 ° C. melt temperature to stimulate poor conditions. Molded test specimens were color measured in a CIE L ^* a ^* b ^* space using a MacBeth 7000 spectrometer for color measurements. Values for delta E, representing color differences between samples molded at 260 ° C. and 320 ° C., were 3.3 in the comparative example and 1.59 in the example containing the rubber-modified thermoplastic resin prepared as in Example 9. .

Example 34 and Comparative Example

A composition comprising the following components was prepared: 50 pbw of bisphenol A polycarbonate having a weight average molecular weight of about 28,000 to about 36,000 g / mol relative to the polystyrene standard; 27 pbw of bisphenol A polycarbonate having a weight average molecular weight of about 18,000 to about 23,000 g / mol relative to the polystyrene standard; And 9.5 parts by weight of suspension-prepared SAN (derived from 75% styrene and 25% acrylonitrile). The composition further included 13.5 parts by weight of a rubber-modified thermoplastic prepared as in Example 9. In addition, the composition is 0.5 part by weight of a mold release agent and a heat stabilizer; 12 parts by weight of coated titanium dioxide; And 0.1 parts by weight of other pigments. The composition in this example was prepared by dry blending the components in a mixer and then extruding using typical processing equipment. The extrudate was pelleted, dried and molded. Having the same composition, except using a rubber-modified thermoplastic resin (referred to as ASA) prepared by grafting 45 pbw of poly (butyl acrylate) to 36.5 pbw of styrene and 19 pbw of acrylonitrile in a single step Comparative Example (C.Ex.) was prepared. Test specimens were molded at 260 ° C. melt temperature and further molded at 320 ° C. melt temperature to stimulate poor conditions. Molded test specimens were color measured in a CIE L ^* a ^* b ^* space using a MacBeth 7000 spectrometer for color measurements. For the values for delta E, which shows the color difference between the samples molded at 260 ° C. and 320 ° C., it was 3.34 in the comparative example and 1.78 in the example containing the rubber-modified thermoplastic resin prepared as in Example 9 .

Although the invention has been described and described in typical embodiments, it should not be considered as limited to the details given, as various changes and alternatives may occur without departing from the spirit of the invention. As such, further modifications and equivalents of the inventions disclosed herein may occur to those skilled in the art using only routine experimentation, and all such modifications and equivalents are defined by the spirit and scope of the invention as defined by the appended claims below. It is thought to belong to the range. All patents and patent applications cited herein are hereby incorporated by reference.

Claims (43)

(i) one or more polycarbonates; (ii) optionally, at least one additional thermoplastic resin different from the polycarbonate; And (iii) at least one rubber-modified thermoplastic resin comprising a discontinuous elastomeric phase dispersed in a rigid thermoplastic phase, At least a portion of the hard thermoplastic phase is grafted onto the elastomer and the hard thermoplastic phase comprises at least one vinyl aromatic monomer, at least one monoethylenically unsaturated nitrile monomer, and (C ₁ -C ₁₂ ) alkyl- and aryl- A composition comprising structural units derived from one or more monomers selected from (meth) acrylate monomers. The method of claim 1, Wherein said polycarbonate comprises structural units derived from at least one dihydroxy aromatic hydrocarbon represented by formula (I) Formula I HO --- D --- OH Wherein D is a divalent aromatic radical having the structure of formula II: Formula II

[Wherein, A ¹ is selected from the group consisting of aromatic groups, phenylene, biphenylene and naphthylene; E is alkylene, alkylidene, methylene, ethylene, ethylidene, propylene, propylidene, isopropylidene, butylene, butylidene, isobutylidene, amylene, amylene, isoamidene, cycloaliphatic Group, cyclopentylidene, cyclohexylidene, 3,3,5-trimethylcyclohexylidene, methylcyclohexylidene, 2- [2.2.1] -bicycloheptylidene, neopentylidene, Cyclopentadidecylidene, cyclododecylidene, adamantylidene; Sulfur-containing linkers, sulfides, sulfoxides, sulfones; Phosphorus-containing linkers, phosphinyl, phosphonyl; Ether connector; Carbonyl groups; Tertiary nitrogen groups; Silicon-containing linkers, silanes, siloxy; And aromatic linkages, tertiary nitrogen linkages, linked by alkylene or alkylidene with other moieties; Ether connector; Carbonyl linkers; Silicon-containing linkers, silanes, siloxy; Sulfur-containing linkers, sulfides, sulfoxides, sulfones; At least two alkylene or alkylidene groups selected from the group consisting of phosphorus-containing linking groups, phosphinyl or phosphonyl; R ¹ is independently at each occurrence a monovalent hydrocarbon group, alkenyl, allyl, alkyl, aryl, aralkyl, alkaryl, cycloalkyl, halogen-substituted monovalent hydrocarbon group, fluoro-substituted monovalent hydrocarbon group , A chloro-substituted monovalent hydrocarbon group, dichloroalkylidene and gem-dichloroalkylidene; Y ¹ is independently at each occurrence an inorganic atom, halogen, fluorine, bromine, chlorine, iodine; Inorganic groups, nitro, containing one or more inorganic atoms; Organic groups, monovalent hydrocarbon groups, alkenyl, allyl, alkyl, C ₁ -C ₆ alkyl, aryl, aralkyl, alkaryl, cycloalkyl and oxy groups OR ² , wherein R ² is alkyl, aryl, aralkyl Is a monovalent hydrocarbon group selected from the group consisting of alkaryl or cycloalkyl); "m" is any integer greater than or equal to 0 and up to the number of substitutable hydrogens on A ¹ acceptable for substitution; "p" is any integer greater than or equal to 0 and up to the number of substitutable hydrogens on E that are acceptable for substitution; "t" is an integer of 1 or more; "s" is an integer of 0 or 1; "u" is any integer containing 0.] The method of claim 1, The polycarbonate is bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, 1, 4-di Hydroxybenzene, 4,4'-oxydiphenol, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4 '-(3,3,5-trimethylcyclohexylidene) Diphenols; 4,4'-bis (3,5-dimethyl) diphenol, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane; 4,4-bis (4-hydroxyphenyl) heptane; 2,4'-dihydroxydiphenylmethane; Bis (2-hydroxyphenyl) methane; Bis (4-hydroxyphenyl) methane; Bis (4-hydroxy-5-nitrophenyl) methane; Bis (4-hydroxy-2,6-dimethyl-3-methoxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; 1,2-bis (4-hydroxyphenyl) ethane; 1,1-bis (4-hydroxy-2-chlorophenyl) ethane; 2,2-bis (3-phenyl-4-hydroxyphenyl) propane; 2,2-bis (4-hydroxy-3-methylphenyl) propane; 2,2-bis (4-hydroxy-3-ethylphenyl) propane; 2,2-bis (4-hydroxy-3-isopropylphenyl) propane; 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane; 3,5,3 ', 5'-tetrachloro-4,4'-dihydroxyphenyl) propane; Bis (4-hydroxyphenyl) cyclohexyl methane; 2,2-bis (4-hydroxyphenyl) -l-phenylpropane; 2,4'-dihydroxyphenyl sulfone; Dihydroxy naphthalene; 2,6-dihydroxy naphthalene; Hydroquinone; Resorcinol; C _1-3 alkyl substituted resorcinol, methylresorcinol, catechol; 1,4-dihydroxy-3-methylbenzene; 2,2-bis (4-hydroxyphenyl) butane; 2,2-bis (4-hydroxyphenyl) -2-methylbutane; 1,1-bis (4-hydroxyphenyl) cyclohexane; 4,4'-dihydroxydiphenyl; 2- (3-methyl-4-hydroxyphenyl-2- (4-hydroxyphenyl) propane; 2- (3,5-dimethyl-4-hydroxyphenyl) -2- (4-hydroxyphenyl Propane; 2- (3-methyl-4-hydroxyphenyl) -2- (3,5-dimethyl-4-hydroxyphenyl) propane; bis (3,5-dimethylphenyl-4-hydroxy Phenyl) methane; 1,1-bis (3,5-dimethylphenyl-4-hydroxyphenyl) ethane; 2,2-bis (3,5-dimethylphenyl-4-hydroxyphenyl) propane; 2, 4-bis (3,5-dimethylphenyl-4-hydroxyphenyl) -2-methylbutane; 3,3-bis (3,5-dimethylphenyl-4-hydroxyphenyl) pentane; 1,1- Bis (3,5-dimethylphenyl-4-hydroxyphenyl) cyclopentane; 1,1-bis (3,5-dimethylphenyl-4-hydroxyphenyl) cyclohexane; bis (3,5-dimethylphenyl 4-hydroxyphenyl) sulfoxide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethylphenyl-4-hydroxyphenyl) sulfide; 3- (4-hydroxy Oxyphenyl) -1,1 , 3-trimethylindan-5-ol; 1- (4-hydroxyphenyl) -1,3,3-trimethylindan-5-ol; 2,2,2 ', 2'-tetrahydro-3, From the group consisting of 3,3 ', 3'-tetramethyl-1,1'-spirobibi [1H-indene] -6,6'-diol and a mixture comprising said at least one dihydroxy-aromatic compound A composition comprising structural units derived from at least one dihydroxy aromatic hydrocarbon selected. The method of claim 1, Wherein said polycarbonate comprises structural units derived from one or more dihydroxy aromatic hydrocarbons represented by the following general formula (III): Formula III

Where Each R ⁵ is independently hydrogen, chlorine, bromine or a C _1-30 monovalent hydrocarbon or hydrocarbonoxy group, Z is hydrogen, chlorine or bromine, respectively, and at least one Z is chlorine or bromine. The method of claim 1, Wherein said polycarbonate comprises structural units derived from one or more dihydroxy aromatic hydrocarbons represented by Formula IV: Formula IV

Where Each R ⁴ is independently hydrogen, chlorine, bromine or a C _1-30 monovalent hydrocarbon or hydrocarbonoxy group, R ^g and R ^h are each independently hydrogen or a C _1-30 hydrocarbon group. The method of claim 5, The composition wherein the dihydroxy aromatic hydrocarbon comprises bisphenol A. The method of claim 1, And wherein said polycarbonate has a weight average molecular weight of about 18,000 to about 40,000 g / mol when measured against polystyrene standards. The method of claim 1, Wherein said polycarbonate comprises a mixture of two or more polycarbonates having different weight average molecular weights. The method of claim 8, Wherein said mixture comprises a weight average molecular weight of about 18,000 to about 23,000 g / mol polycarbonate in combination with a weight average molecular weight of about 28,000 to about 36,000 g / mol polycarbonate. The method of claim 1, Wherein the polycarbonate is present in an amount of about 5 to about 95 weight percent based on the total composition weight. The method of claim 1, Further thermoplastic resins are (meth) acrylate homopolymers and copolymers, methyl methacrylate-butyl acrylate copolymers, methyl methacrylate-ethyl acrylate copolymers, homopolymers and copolymers of styrene and alkylstyrene , Styrene-acrylonitrile (SAN) copolymer, alpha-methylstyrene-acrylonitrile (AMSAN) copolymer, methyl methacrylate-styrene-acrylonitrile (MMA-SAN) terpolymer , Methyl methacrylate / alpha-methylstyrene / acrylonitrile (MMA-AMSAN) terpolymer, and mixtures thereof. The method of claim 11, Wherein said additional thermoplastic resin is present in the composition in an amount of about 1 to about 80 weight percent based on the total composition weight. The method of claim 1, Wherein said elastomeric phase comprises a polymer having structural units derived from at least one (C ₁ -C ₁₂ ) alkyl (meth) acrylate monomer. The method of claim 13, Wherein said alkyl (meth) acrylate monomer is butyl acrylate. The method of claim 1, Wherein said elastomeric phase further comprises structural units derived from at least one polyethyleneic unsaturated monomer. The method of claim 15, The polyethylene unsaturated monomers include butylene diacrylate, divinyl benzene, butene diol dimethacrylate, trimethylolpropane tri (meth) acrylate, allyl methacrylate, diallyl methacrylate and diallyl male. A composition selected from the group consisting of eight, diallyl fumarate, diallyl phthalate, triallyl methacrylate, triallyl isocyanurate, triallyl cyanurate, acrylate of tricyclodecenyl alcohol, and mixtures thereof . The method of claim 1, Wherein said elastomeric phase comprises from about 10 to about 80 weight percent rubber-modified thermoplastic resin. The method of claim 1, Wherein said elastomeric phase comprises from about 35 to about 80 weight percent of a rubber-modified thermoplastic resin. The method of claim 1, Said elastomeric phase comprising particles initially selected from the group consisting of a mixture of particles having at least two number average particle size distributions and particles having a broadband size distribution having particles of size about 50 to about 1000 nm. The method of claim 19, Wherein the two number average particle size distributions are each present in a range from about 80 to about 500 nm. The method of claim 1, At least about 5 to about 90 weight percent of the hard thermoplastic phase is chemically grafted onto the elastomer, based on the total amount of the hard thermoplastic phase in the composition. The method of claim 1, The hard thermoplastic phase comprises styrene, acrylonitrile and methyl methacrylate; Alpha-methyl styrene, acrylonitrile and methyl methacrylate; Or structural units derived from styrene, alpha-methyl styrene, acrylonitrile and methyl methacrylate. The method of claim 22, And wherein the weight / weight ratio of styrene, alpha-methyl styrene, or mixtures thereof to acrylonitrile is from about 1.5: 1 to about 4: 1. The method of claim 22, A composition wherein the weight percent / weight percent ratio of styrene, alpha-methyl styrene or mixtures thereof to acrylonitrile is from about 2: 1 to about 3: 1. The method of claim 22, And wherein the weight / weight ratio of styrene, alpha-methyl styrene, or mixtures thereof to acrylonitrile is about 2.6: 1. The method of claim 22, A composition wherein the weight percent / weight percent ratio of methyl methacrylate to vinyl aromatic monomer and monoethylenically unsaturated nitrile monomer is from about 4: 1 to about 1: 4. The method of claim 1, The amount of (C ₁ -C ₁₂ ) alkyl- or aryl- (meth) acrylate monomers used for grafting to the rubber substrate is from about 70 to about 2 weight based on the total amount of all monomers used for grafting % Composition. The method of claim 1, And at least one additive selected from the group consisting of colorants, dyes, pigments, lubricants, stabilizers, mold release agents, fillers and mixtures thereof. Based on the weight of the total composition, (i) about 5 to about 95 weight percent of one or more polycarbonates comprising structural units derived from bisphenol A; (ii) (meth) acrylate homopolymers and copolymers, methyl methacrylate-butyl acrylate copolymers, methyl methacrylate-ethyl acrylate copolymers, homopolymers and copolymers of styrene and alkylstyrene, styrene Ethylene-acrylonitrile (SAN) copolymer, alpha-methylstyrene-acrylonitrile (AMSAN) copolymer, methyl methacrylate-styrene-acrylonitrile (MMA-SAN) terpolymer, methyl About 1 to about 80 weight percent of at least one additional thermoplastic resin different from a polycarbonate selected from the group consisting of methacrylate / alpha-methylstyrene / acrylonitrile (MMA-AMSAN) terpolymers, and mixtures thereof; And (iii) at least one rubber-modified thermoplastic resin comprising a discontinuous elastomeric phase dispersed in a rigid thermoplastic phase, At least a portion of the hard thermoplastic phase is grafted onto an elastomeric phase, the elastomeric phase comprising structural units derived from butyl acrylate; The hard thermoplastic phase comprises styrene, acrylonitrile and methyl methacrylate; Alpha-methyl styrene, acrylonitrile and methyl methacrylate; Or structural units derived from styrene, alpha-methyl styrene, acrylonitrile and methyl methacrylate; The weight / weight ratio of styrene, alpha-methyl styrene or mixtures thereof to acrylonitrile is from about 1.5: 1 to about 4: 1; And wherein the weight percent / weight percent ratio of methyl methacrylate to other monomers is from about 4: 1 to about 1: 4. The method of claim 29, And at least one additive selected from the group consisting of colorants, dyes, pigments, lubricants, stabilizers, mold release agents, fillers and mixtures thereof. (i) at least one polycarbonate comprising structural units derived from bisphenol A; (ii) (meth) acrylate homopolymers and copolymers, methyl methacrylate-butyl acrylate copolymers, methyl methacrylate-ethyl acrylate copolymers, homopolymers and copolymers of styrene and alkylstyrene, styrene Ethylene-acrylonitrile (SAN) copolymer, alpha-methylstyrene-acrylonitrile (AMSAN) copolymer, methyl methacrylate-styrene-acrylonitrile (MMA-SAN) terpolymer, methyl At least one further thermoplastic resin different from the polycarbonate selected from the group consisting of methacrylate / alpha-methylstyrene / acrylonitrile (MMA-AMSAN) terpolymers, and mixtures thereof; And (iii) at least one rubber-modified thermoplastic resin comprising a discontinuous elastomeric phase dispersed in a rigid thermoplastic phase, At least a portion of the hard thermoplastic phase is grafted onto the elastomer, The elastomeric phase comprises a polymer having structural units derived from one or more (C ₁ -C ₁₂ ) alkyl (meth) acrylate monomers, Rubber-modified thermoplastics (a) at least one monomer is selected from the group consisting of vinyl aromatic monomers, at least one monomer is selected from the group consisting of monoethylenically unsaturated nitrile monomers, and optionally at least one monomer is selected from (C ₁ -C ₁₂ ) alkyl ( A first step of polymerizing a monomer mixture selected from the group consisting of meth) acrylate monomers in the presence of an elastomeric phase; And (b) one or more subsequent steps of polymerizing one or more monomers in the presence of the elastomeric phase from the first step (a), wherein the one or more monomers are selected from the group consisting of vinyl aromatic monomers, monoethylenically unsaturated A composition prepared by a method comprising the step of comprising at least one monomer selected from the group consisting of nitrile monomers, and optionally at least one monomer selected from the group consisting of (C ₁ -C ₁₂ ) alkyl (meth) acrylate monomers. . The method of claim 31, wherein Wherein the polycarbonate is present in an amount of about 5 to about 95 weight percent based on the total composition weight. The method of claim 31, wherein Wherein the alkyl (meth) acrylate monomer on the elastomer comprises butyl acrylate. The method of claim 31, wherein Wherein the alkyl (meth) acrylate monomer polymerized in the presence of said elastomeric phase is present in step (b). The method of claim 31, wherein A composition wherein the amount of alkyl- (meth) acrylate monomers used for grafting to the rubber substrate is from about 70 to about 2 weight percent based on the total amount of all monomers used for grafting. The method of claim 31, wherein Wherein said alkyl (meth) acrylate monomer polymerized in the presence of said elastomeric phase is methyl methacrylate. The method of claim 31, wherein Wherein said additional thermoplastic resin is present in the composition in an amount of about 1 to about 80 weight percent based on the total composition weight. The method of claim 31, wherein And at least one additive selected from the group consisting of colorants, dyes, pigments, lubricants, stabilizers, mold release agents, fillers and mixtures thereof. An article comprising the composition of claim 1. An article comprising the composition of claim 29. An article comprising the composition of claim 31. (i) one or more polycarbonates; (ii) optionally, at least one additional thermoplastic resin different from the polycarbonate; And (iii) at least one rubber-modified thermoplastic resin comprising a discontinuous elastomeric phase dispersed in a rigid thermoplastic phase, At least a portion of the hard thermoplastic phase is grafted onto the elastomeric phase, the hard thermoplastic phase being at least one vinyl aromatic monomer, at least one monoethylenically unsaturated nitrile monomer, and (C ₁ -C ₁₂ ) alkyl- and aryl- ( A process for preparing a composition comprising structural units derived from one or more monomers selected from meth) acrylate monomers, Combining the components under intimate mixing conditions. (i) one or more polycarbonates; (ii) optionally, at least one additional thermoplastic resin different from the polycarbonate; And (iii) at least one rubber-modified thermoplastic resin comprising a discontinuous elastomeric phase dispersed in a rigid thermoplastic phase, In an article made from a thermoplastic composition wherein at least a portion of the hard thermoplastic phase is grafted onto an elastomer and the hard thermoplastic phase comprises at least one vinyl aromatic monomer and at least one monoethylenically unsaturated nitrile monomer, color loss or gloss loss. As a method of improving the resistance to Incorporating a structural unit derived from at least one monomer selected from the group consisting of (C ₁ -C ₁₂ ) alkyl- and aryl- (meth) acrylate monomers in the hard thermoplastic phase.